Aryl diphosphines and catalysts containing the same

ABSTRACT

The present invention provides novel aryl diphosphines having the formula ##STR1## wherein X, Y, R 1-18 , m, m&#39; and n are defined herein, and which can be complexed with a transition metal to form a novel catalyst useful in such applications as hydroformylation.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention is directed to novel water-soluble sulfonated aryldiphosphines, catalysts containing the same, processes for preparingsuch diphosphines and catalysts, and processes for using such catalysts.

2. General Background and Prior Art Problems

One of the major problems of homogeneous catalysis is the separation ofcatalyst from product. The lifetime of a catalyst in an industrialprocess is greatly affected by the means of separation. It has beenshown that a two phase system with water soluble phosphines as ligandscan be very effective to achieve easy recycling of catalysts. However,the reactivity of the water soluble catalyst is somewhat limited by thesolubility of the organic substrate in aqueous phase. The synthesis ofwater soluble phosphines has reached a stage that it is possible now totailor the structure of a phosphine for improved reactivity whileretaining excellent water solubility for good catalyst separation.

A widely used method for synthesizing water soluble phosphines is directsulfonation to introduce one or more sulfonate groups onto a phenyl ringbonded to phosphorus. Unfortunately the direct sulfonation oftenrequires harsh conditions and long reaction times. The reaction producessignificant amount of phosphine oxide along with phosphines withdifferent degrees of sulfonation. All these complicate the purificationof the sulfonated products and contribute to a poor yield of sulfonationproducts. Therefore, the conventional direct sulfonation is not verysuitable for chiral and non-chiral water soluble phosphine synthesis,since a large portion of expensive chiral phosphine is going to besacrificed in direct sulfonation. For this reason perhaps, the yieldsfor the direct sulfonation of chiral phosphines such as BDPP and BINAPare not reported.

One of the most interesting chiral biphosphines is (R)-(+)- and(S)-(-)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl, BINAP. It showsexceptional enantioselectivity for asymmetric hydrogenations. The directsulfonation of BINAP results in a mixture of phosphines with variousdegrees of sulfonation. The uncertainty of the sulfonated sites causesdifficulties for characterization of the ligand and its metal complexes.

Thus, there is a need for new compounds which are water soluble, exhibitoutstanding surface active properties in two phase catalysis,particularly in the area of two phase hydroformylation of olefins suchas 1-octene, and are easily accessible by mild sulfonation conditions.

DESCRIPTION OF THE PRIOR ART

The following prior art references are disclosed in accordance with theterms of 37 CFR 1.56, 1.97, and 1.93.

U.S. Pat. No. 5,057,618 discloses complex compounds containingsulfonated phenyl phosphines.

U.S. Pat. No. 5,274,183 discloses water-soluble sulfonated diphosphines.

Other references pertinent to diphosphine ligands, processes forpreparing the same, and catalysts containing the same include:

1. W. A. Herrmann, C. W. Kohlpaintner, Angew. Chem. Int. Ed. Engl.,1993, 32, 1524-1544.

2. R. Noyori, Chem. Soc. Rev., 1989, 18, 187.

3. R. Noyori, M. Kitamura, Modern Synthetic Methods, Vol. 5, R.Scheffold ed., Berlin: Springer-Verlag, 1989, 115-198.

4. R. Noyori, Chemtech, June 1992, 360-367.

5. Y. Amranni, L. Lecomte, D. Sinou, J. Bakos, I. Toth, B. Heil,Organometallics, 1989, 8, 542-547.

6. K. Wan, M. E. Davis, J. C. S., Chem. Commun., 1993, 1263.

7. H. Ding, B. E. Hanson, T. Bartik, B. Bartik, Organometallics, 1994,13, 3761.

8. H. Ding, B. E. Hanson, Angew. Chem. Int. Ed. Engl., 107, 1728 (1995).

9. A. S. C. Chan, Chemtech, March 1993, 47-51.

10. N. Sayo, H. Kumobayashi, S. A. Kutagawa, R. Noyori, H. Takaya,EP-A-0 295 890 (19 6 1987).

11. W. S. Knowles, Acc. Chem. Res., 1983, 16, 106.

12. W. S. Knowles, W. O. Christopher, K. E. Koening, C. F. Hobbs, Adv.Chem. Ser., 1982, 196, 325.

13. T. Ohta, H. Takaya, M. Kitamura, K. Nagai, R. Noyori, J. Org. Chem.,1987, 52, 3174.

14. M. Fiorini, G. M. Giongo, J. Mol. Catal., 1979, 5, 303.

15. M. Fiorini, G. M. Giongo, ibid, 1980, 7, 411.

16. J. E. Babin, G. T. Whiteker, World Patent, WO 93/03839, 1993.

17. H. Ding, B. E. Hanson, J. C. S., Chem. Commun., 1994,2747.

18. M. Vondenhof and J. Mattay, Tetrahedron lett., 1990, 31, 985.

19. J Org. Chem., D. Cai, J. F. Payack, D. R. Bender, D. L. Hughes, T.R. Verhoeven and P. J. Reider, 1994, 59, 7180.

20. T. Maninaran, T-C. Wu, W. D. Klobucar, C. H. Kolich, G. P. Stahly,F. R. Fronczek and S. E. Watkins, Organometallics, 1993, 12, 1467.

21. K. Wan and M. E. Davis, J. Catal, 1994, 148, 1.

22. D. Cai, J. F. Payack, D. R. Bender, D. L. Haghes, T. R. Verhoeven,P. J. Reider, J. Org. Chem., 1994, 59, 7180.

All of the above cited prior art and any other references mentionedherein are incorporated herein by reference in their entirety.

SUMMARY OF THE INVENTION

The present invention provides novel aryl diphosphines having theformula ##STR2## wherein X, Y, R₁₋₁₈, m, m' and n are defined herein,and which can be complexed with a transition metal to form a novelcatalyst useful in such applications as hydroformylation.

DETAILED DESCRIPTION OF THE INVENTION

The present invention provides, in part, a novel aryl diphosphine havingthe formula ##STR3## wherein (a) X and Y are each independently selectedfrom the group consisting of alkyl C₁ -C₂₀, alkenyl C₁ -C₂₀, alkynyl C₁-C₂₀, phenyl, naphthyl, --NR-- (where R is H, alkyl C₁ -C₂₀ and phenyl),oxygen and sulfur; (b) m and m' are each separate integers of 0 or 1;(c) R₁ -R₈ are each independently selected from the group consisting ofhydrogen, halogen, nitro, amino, alkyl C₁ -C₂₀, alkoxy, hydroxy,--C(O)--OR, --CN, --SO₃ M, --N.sup.⊕ (R)₃ X.sup.⊖ (where X.sup.⊖ is ahalide), and aryl; (d) R₁ and R₂, R₂ and R₃, R₃ and R₄, R₅ and R₆, R₆and R₇, R₇ and R₈ may also (in addition to the above) form a cyclic ringcontaining a total of 2 to 6 atoms selected from the group consisting ofcarbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms, and mixturesthereof, with the proviso that said ring can be substituted orunsubstituted; (e) R₉ -R₁₂ and R₁₄ -R₁₈ are each independently selectedfrom the group consisting of hydrogen, halogen, --SO₃ M where M is analkali metal (e.g. Na, K, Li, Rb, Cs), alkaline earth metals such as Mgand Ca, and N(R)₄.sup.⊕ (where R is H, alkyl C₁ -C₂₀, phenyl), alkyl C₁-C₂₀, --CO₂ M, --N.sup.⊕ (R)₃ X.sup.⊖ (where X.sup.⊖ is a halide), --CN,--OR, --C(O)--OR, and --P(R)₂, where R is H, alkyl C₁ -C₂₀, and phenyl;(f) R₁₃ is selected from the group consisting of a straight chain orbranched chain alkyl C₁ -C₂₀, alkenyl C₁ -C₂₀, alkynyl C₁ -C₂₀, phenyl,naphthyl, anthracyl, and substituted phenyl, naphthyl, and anthryl; and(g) n is an integer from 0 to 20.

In formula I above, the substituents on the phenyl, naphthyl, anthracyland the cyclic ring are selected, for example, from the group consistingof hydrogen, nitro, halogen, alkoxy, alkyl C₁ -C₂₀, carboxylate, amino,amide, silyl, and siloxyl.

In order to provide the greatest water solubility, at least one of R₁-R₁₂ and R₁₄ -R₁₈ is --SO₃ M.

In the above definitions of X, Y, and R₁ -R₁₈, the term halogen includeschlorine, fluorine, bromine and iodine. The term alkyl includes straightand branch chained saturated hydrocarbon radicals having from 1 to 20carbon atoms such as, for example, methyl; ethyl; 1-methylethyl;1,1,-dimethylethyl; propyl; 2-methylpropyl; butyl; pentyl; hexyl and thelike. The term alkoxy includes the alkyl definition above plus theoxygen atom e.g. methoxy, ethoxy, isopropoxy, tert-butoxy, and the like.Term aryl includes phenyl, naphthyl, anthryl, phenanthryl and the like.

As used herein, the term "substituted" is contemplated to include allpermissible substituents of organic compounds. In a broad aspect, thepermissible substituents include acyclic and cyclic, branched andunbranched, carbocyclic and heterocyclic, aromatic and nonaromaticsubstituents of organic compounds. Illustrative substituents include,for example, those described herein. The permissible substituents can beone or more and the same or different for appropriate organic compounds.For purposes of this invention, the heteroatoms such as nitrogen mayhave hydrogen substituents and/or any permissible substituents oforganic compounds described herein which satisfy the valencies of theheteroatoms. This invention is not intended to be limited in any mannerby the permissible substituents of organic compounds.

In another facet of the present invention, the ligands/diphosphines offormula I are complexed with a transition metal (M') to yield newcatalysts having the formula ##STR4## wherein X, Y, R₁₋₁₈, M, m, m' andn are the same as described in formula I above, and M' is selected fromthe group consisting of chromium, manganese, iron, cobalt, nickel,copper, molybdenium, technetium, ruthenium, rhodium, palladium, silver,cadmium, tungsten, rhenium, osmium, indium, platinum, gold, and mercury;L is any ligand which can be bound to M'; and x is an integer of 0 to 7.

Formula II shows that M' is complexed with both phosphorus atoms in abidentate form; however, it is also within the scope of the presentinvention that the metal M' is only complexed with one phosphorus atomin a monodentate form as shown below: ##STR5## wherein X, Y, R₁₋₁₈, M,M', m, m', n, L and x are the same as in formula II.

To enhance the formation of compounds falling within formula (III), onephosphorus atom can be oxidized, sulfidized, or quarternized to preventcoordination.

Thus the single P-atom moiety can have the partial formula ##STR6##wherein R is alkyl C₁ -C₂₀ (straight or branched chain), phenyl(substituted or unsubstituted) and naphthyl (substituted orunsubstituted); and X.sup.⊖, in this case, is a halide such as F, Br, I,and Cl, or tosylate (═CF₃ SO₃.sup.⊖).

Specific categories of the novel catalysts where the non-monodentatephosphorus atom is oxidized, sulfidized, or quaternized are shown below:##STR7##

In these formulae, L is any ligand which can be complexed with M', i.e.bound to the central atom in the complex compound. Typical ligands whichfall within this category include, without limitiation, CO, NO, PF₃, H₂O, S, halogen (Cl, F, Br, I), PF⁻ ₆, CN⁻, BF⁻ ₄, hydrides, π-aromaticligands such cyclopentadienyl, π-olefin ligands such as cyclooctadiene,π-acetylene ligands such as diphenylacetylene, and other phosphineligands.

In these formulae, M' represents any metal, i.e. a transition metalwhich can be bound or complexed with the phosphorus atom(s). Such metalis from the groups IB, VII A and VIII A of the Periodic Table (IuPACversion numbers group 1-18). Thus, M' includes, without limitationchromium, manganese, iron, cobalt, nickel, copper, molybdenium,technetium, ruthenium, rhodium, palladium, silver, cadmium, tungsten,rhenium, osmium, indium, platinum, gold, and mercury.

In general, the novel aryl diphosphine ligands are prepared by a processwhich comprises the steps of (a) subjecting an arylphosphine halide tometallation conditions including suitable temperature and pressure toform an arylphosphinide, and (b) subjecting said arylphosphinide tocoupling conditions, including suitable temperature and pressure, in thepresence of an organic halide to form said aryl diphosphine.

The starting material is an aryl-phosphine halide having the formula##STR8## wherein R₉ -R₁₈ and n are the same as disclosed for formula Iabove, except --SO₃ M is not present.

The metallation conditions are those which promote the complexing of ametal from Group I and Group II of the Periodic Table of Elements to thephosphorus atom. The metal is, for example, lithium, sodium, potassium,rubidium, cesium, magnesium, and calcium. The molar ratio of metal tophosphine halide can be any amount as long as the reaction proceeds toyield the desired result. In general however, such ratio is about 2:1.The temperatures and pressures are not critical, however, thetemperature range is from about 0° C. to about 100° C., or greater. Thepressure can be sub-atmospheric, atmospheric or super-atmospheric. Thereaction time is not critical.

Thus, this metallation proceeds as follows:

    X--P(Aryl).sub.2 +2M→

    M--P(aryl).sub.2 +MX

(arylphosphinide)

where X is a halide or another electron withdrawing group (EWG) and M isa metal.

The end result, as shown above, is an arylphosphinide. Thisarylphosphinide is then subjected to coupling conditions as shown below:##STR9##

EWG is an electron withdrawing group such as a halide like Br or --OSO₂R where R is alkyl C₁ -C₂₀, preferably fluorinated such as CF₃, C₂ F₅etc.

The coupling conditions are not critical and can be any temperature andpressure as long as the desired end result is achieved. The temperaturerange is generally from about 0° C. to about 100° C. or greater. Thepressure can be sub-atmospheric, atmospheric, or super-atmospheric. Thereaction time is not critical. The halide is Cl, Br, F, or I, andgenerally is Br.

In another facet of the present invention, the diphosphine can also beprepared by reacting the phosphine H--P (aryl)₂ with ##STR10## to yieldthe diphosphine with the assistance of a coupling catalyst like NiCl₂(dppe), where ##STR11## (dppe) is C₆ H₅)₂ P--CH₂ --CH₂ --P(C₆ H₅)₂,Bis(diphenylphosphino) ethane. Thus, an equation for this reaction is asfollows: ##STR12##

In order to provide the aryl diphosphine with water-solublecharacteristics, the diphosphine of Formula (I), without the --SO₃ Mgroup, is subjected to acid sulfonation and base conditions as shownbelow: ##STR13##

The acid, such as H₂ SO₄, provides the --SO₃.sup.⊖ groups and the base,such as NaOH, provides a metal, M, such as sodium. In this fashion, ithas unexpectedly been found that the sulfonation can be carried out inan easy manner (i.e. without significant oxidation or degradiationreactions at very mild conditions), as compared to the prior art, andthat the end result is a water-soluble aryl diphosphine which can beused (along with a metal for complexing to form a catalyst) in numerousorganic processes. The temperatures, pressures and reaction times ofthis sulfonation are not critical.

It is to be understood that the processes as described above can employa solvent to facilitate the reaction mechanism. Such solvents are, ingeneral, organic and include, without limitation, THF, Et₂ O, alkanesand/or mixtures thereof.

Scheme 1 shows an example of the preparation of a water-soluble aryldiphosphane ligand, 2,2'-Bis{dip-(3-p-sulfonatophenylpropyl)phenyl!phosphinomethyl}-1,1'-biphenyl(BISBI-C₃ -TS). ##STR14##

The novel catalysts sometimes referred to as a "metal-ligand complexcatalysts" of the present invention are prepared either in situ or byreacting the water-soluble aryl diphosphine ligand with, for example,Rh(CO)₂ acac (acac=acetylacetonate) in an organic liquid/solvent such asmethanol.

Although the novel catalysts have a wide variety of applications anduses in numerous organic processes, one facet of the present inventionrelates to asymmetric synthesis in which, e.g. a prochiral or chiralcompound is reacted in the presence of optically active, metal-ligandcomplex catalyst, in enantiomerically active form, to produce anoptically active product.

Specifically, it has been unexpectedly found that the novel catalysts,disclosed in the earlier part of this specification, can effectasymmetric synthesis in various processes with various substrates toproduce a material which is optically active.

The asymmetric synthesis processes of this invention are useful for theproduction of numerous optically active compounds, e.g., aziridines,cyclopropanes, aldehydes, alcohols, ethers, esters, amines, amides,carboxylic acids and the like, which have a wide variety ofapplications.

This part of the subject invention encompasses the carrying out of anyknown conventional synthesis in an asymmetric fashion with the noveloptically active metal-ligand complex catalyst as disclosed herein. Someprocesses of this invention stereoselectively produce an enantiomer.

The permissible achiral, prochiral or chiral starting material reactantsencompassed by part of the processes of this invention are, of course,chosen depending on the particular synthesis desired. Such startingmaterials are well known in the art and can be used in conventionalamounts in accordance with conventional methods. Illustrative startingmaterial reactants include, for example, substituted and unsubstitutedaldehydes (intramolecular hydroacylation, aldol condensation), prochiralolefins (hydroformylation, hydrogenation, hydrocyanation,hydrosilylation, aziridination, hydroamidation, aminolysis,cyclopropanation, hydroboration, Diels-Alder reaction, codimerization),ketones (hydrogenation, hydrosilylation, aldol condensation, transferhydrogenation, allylic alkylation), epoxides (hydrocyanation,nucleophilic ring opening reaction), alcohols (carbonylation) acyl andaryl chlorides (decarbonylation), a chiral Grignard reagent (Grignardcross coupling) and the like.

The novel catalysts of the present invention thus have utility in a widevariety of chemical processes, and particularly, in asymmetric synthesisreaction which include, without limitation; hydroxylation;cyclopropanation; aziridination; Diels-Alder reactions; cycloaddition,Michael addition; Aldol reaction; hydroboration; olefin and ketonehydrosilylation; hydrocyanation; addition of Grignards ororganometallics to aldehydes and ketones; allylic alkylation; Grignardcross coupling; kinetic resolution; hydroamidation; olefinisomerization; aminolysis; hydrogenation; hydroformylation; andhydrocarboxylation.

The amount of catalyst in the reaction medium of a given process of thisinvention need only be that minimum amount necessary to catalyze theparticular organic syntheses process desired. In general, concentrationsin the range of from about 1 ppm to about 10,000 ppm, based on thestarting reactant, should be sufficient for most syntheses processes.For example, in the catalyzed processes of this invention, it isgenerally preferred to employ from about 10 to 1000 ppm and morepreferably from 25 to 750 ppm.

The process conditions employable in the organic processes of thisinvention are, of course, chosen depending on the particular organicsyntheses desired. Such process conditions are well known in the art.All of the organic syntheses processes of this invention can be carriedout in accordance with the conventional procedures known in the art.Illustrative reaction conditions for conducting the asymmetric synthesesprocesses of this invention are described, for example, in Bosnich, B.,Asymmetric Catalysis, Martinus Nijhoff Publishers, 1986 and Morrison,James D., Asymmetric Synthesis, Vol. 5, Chiral Catalysis, AcademicPress, Inc., 1985, both of which are incorporated herein by reference intheir entirety. Depending on the particular process, operatingtemperatures can range from about -80° C. or less to about 500° C. orgreater and operating pressures can range from about 1 psia or less toabout 10,000 psia or greater.

The reaction conditions of effecting, for example, the processes of thisinvention may be those heretofore conventionally used and may comprise areaction temperature of from about -25° C. or lower to about 200° C. orhigher and pressures ranging from about 1 to about 10,000 psia.Moreover, while such other syntheses may be performed under their usualconditions, in general, it is believed that they may be performed atlower temperatures than normally preferred due to the presence of themetal-ligand complex catalysts.

In general, the processes of this invention may be conducted at areaction temperature from about -25° C. or lower to about 200° C. Thepreferred reaction temperature employed in a given process will, ofcourse, be dependent upon the particular starting material andmetal-ligand complex catalyst employed as well as the efficiencydesired.

The processes are conducted for a period of time sufficient to producethe desired products. The exact time employed is dependent, in part,upon factors such as temperature, nature, and proportion of startingmaterials, and the like. The reaction time will normally be within therange of from about one-half to about 200 hours or more, and preferablyfrom less than about 1 to 10 hours.

The processes of this invention may be conducted in the presence of anorganic solvent for the metal-ligand complex catalyst. Depending on theparticular catalyst and reactants employed, suitable organic solventsinclude, for example, alcohols, alkanes, alkenes, alkenes, ethers,aldehydes, ketones, esters, acids, amides, amines, aromatics, and thelike. Any suitable solvent which does not unduly adversely interferewith the syntheses process can be employed and such solvents may includethose heretofore commonly employed in known metal catalyzed processes.Increasing the dielectric constant or polarity of a solvent maygenerally tend to favor increased reaction rates.

Mixtures of one or more different solvents may be employed if desired.It is obvious that the amount of solvent is not critical to the subjectinvention and need only be that amount sufficient to provide thereaction medium with the particular metal concentration desired for agiven process. In general, the amount of solvent when employed may rangefrom about 5% by weight up to about 95% by weight or more, based on thetotal weight of the reaction medium.

The processes of this invention can provide optically active products byhaving very high enantioselectivity and regioselectivity. Enantiomericexcesses of preferably greater than 50% can be obtained by the processesof this invention. The processes of this invention can also be carriedout at highly desirable reaction rates suitable for commercial use.

The desired products may be recovered in most cases by phase separation.Other separation methods include solvent extraction, crystallization,distillation, vaporization, wiped film evaporation, falling filmevaporation, and the like. It may be desired to remove the products fromthe reaction systems as they are formed through the use of trappingagents as described in WO patent 88/08835.

The optically active products produced by the asymmetric synthesesprocesses of this invention can undergo further reaction(s) to afforddesired derivatives thereof. Such permissible derivitization reactionscan be carried out in accordance with conventional procedures known inthe art. Illustrative derivitization reactions include, for example,esterification, oxidation of alcohols to aldehydes, N-alkylation ofamides, addition of aldehydes to amides, nitrile reduction, acylation ofketones by esters, acylation of amines, and the like.

Illustrative of suitable reactants in effecting the processes of thisinvention include by way of example:

    ______________________________________                                               AL         alcohols                                                           PH         phenols                                                            THP        thiophenols                                                        MER        mercaptans                                                         AMN        amines                                                             AMD        amides                                                             ET         ethers                                                             EP         epoxides                                                           ES         esters                                                             H          hydrogen                                                           CO         carbon monoxide                                                    HCN        hydrogen cyanide                                                   HS         hydrosilane                                                        W          water                                                              GR         grignard reagent                                                   AH         acyl halide                                                        UR         ureas                                                              OS         oxalates                                                           CN         carbamates                                                         CNA        carbamic acids                                                     CM         carbonates                                                         CMA        carbonic acids                                                     CA         carboxylic acids                                                   ANH        anhydrides                                                         KET        ketones                                                            OLE        olefins                                                            ACE        acetylenes                                                         HAL        halides                                                            SUL        sulfonates                                                         ALD        aldehydes                                                          NIT        nitriles                                                           HC         hydrocarbons                                                       DZ         diazo compounds                                                    BOR        boranes                                                            ESE        enol silyl ethers                                                  SUD        sulfides                                                    ______________________________________                                    

Illustrative of suitable products prepared by the asymmetric synthesesprocesses of this invention include by way of example:

    ______________________________________                                               AL         alcohols                                                           PH         phenols                                                            THP        thiophenols                                                        MER        mercaptans                                                         AMN        amines                                                             AMD        amides                                                             ET         ethers                                                             ES         esters                                                             H          hydrogen                                                           CO         carbon monoxide                                                    SI         silanes                                                            UR         ureas                                                              OX         oxalates                                                           CN         carbamates                                                         CNA        carbamic acids                                                     CM         carbonates                                                         CMA        carbonic acids                                                     CA         carboxylic acids                                                   ANH        anhydrides                                                         KET        ketones                                                            OLE        olefins                                                            ACE        acetylenes                                                         HAL        halides                                                            ALD        aldehydes                                                          NIT        nitriles                                                           HC         hydrocarbons                                                       CYP        cyclopropanes                                                      ABR        alkylboranes                                                       ADL        aldols                                                             AZ         aziridines                                                  ______________________________________                                    

Illustrative of reactions encompassed within the scope of this inventioninclude, for example, the following reactant/product combinations:

    ______________________________________                                        REACTANT(S)          PRODUCT(S)                                               ______________________________________                                        OLE, CO, H           ALD                                                      OLE, CO, H           CA                                                       ALD                  KET                                                      OLE, ALD             KET                                                      OLE, HC              HC                                                       OLE, CO              CA                                                       OLE, CO, AMN         AMD                                                      OLE                  AZ                                                       OLE, CO, AL          ES                                                       KET, H               AL                                                       EP, H                AL                                                       OLE, AMN             AMN                                                      OLE, AL              ET                                                       AL, CO               CA                                                       AL                   ALD                                                      OLE, HCN             NIT                                                      OLE, HS              SI                                                       OLE, CO, W           CA                                                       OLE                  OLE                                                      GR                   HC                                                       AH                   HAL                                                      OLE, H               HC                                                       OLE, BOR             AL                                                       OLE, BOR             ABR                                                      OLE, DZ              CYP                                                      KET, AL              AL                                                       ALD, ESE             ADL                                                      KET, ESE             ADL                                                      KET, HS              AL                                                       EP, CO, H            ALD                                                      EP, HCN              NIT                                                      ALD                  CA                                                       ______________________________________                                    

As indicated above, the processes of this invention can be conducted ina batch or continuous fashion, with recycle of unconsumed startingmaterials if required. The reaction can be conducted in a singlereaction zone or in a plurality of reaction zones, in series, or inparallel, or it may be conducted batchwise or continuously in anelongated tubular zone or series of such zones. The materials ofconstruction employed should be inert to the starting materials duringthe reaction and the fabrication of the equipment should be able towithstand the reaction temperatures and pressures. Means to introduceand/or adjust the quantity of starting materials or ingredientsintroduced batchwise or continuously into the reaction zone during thecourse of the reaction can be conveniently utilized in the processesespecially to maintain the desired molar ratio of the startingmaterials. The reaction steps may be effected by the incrementaladdition of one of the starting materials to the other. Also, thereaction steps can be combined by the joint addition of the startingmaterials to the metal-ligand complex catalyst. When complete conversionis not desired or not obtainable, the starting materials can beseparated from the product and the recycled back into the reaction zone.

The processes may be conducted in either glass lined, stainless steel orsimilar type reaction equipment. The reaction zone may be fitted withone or more internal and/or external heat exchanger(s) in order tocontrol undue temperature fluctuations, or to prevent any possible"runaway" reaction temperatures.

Finally, the products of the process of this invention have a wide rangeof utility that is well known and documented in the prior art, e.g. theyare especially useful as intermediates for pharmaceuticals, flavors,fragrances, agricultural chemicals, and the like. Illustrativetherapeutic applications include, for example, non-steroidalanti-inflammatory drugs, ACE inhibitors, beta-blockers, analgesics,bronchodilators, spasmolytics, antihistamines, antibiotics, antitumoragents, and the like.

For purposes of this invention, the chemical elements are identified inaccordance with the Periodic Table of the Elements, CAS version,Handbook of Chemistry and Physics, 67th Ed., 1986-87, inside cover. Alsofor purposes of this invention, the term "hydrocarbon" is contemplatedto include all permissible compounds having at least one hydrogen andone carbon atom. In a broad aspect, the permissible hydrocarbons includeacyclic and cyclic, branched and unbranched, carbocyclic andheterocyclic, aromatic and nonaromatic organic compounds which can besubstituted or unsubstituted.

The following specific examples are supplied for the purpose of betterillustrating the invention. These examples are not intended, however, tolimit or restrict the scope of the invention in any way and should notbe construed as providing conditions, parameters, or values which mustbe utilized exclusively in order to practice the present invention.

General Aspects of the Synthesis of Surface Active Phosphines

The overall scheme of preparing the desired compounds is set forth inScheme 2 as a compliment to Scheme 1. The specific steps are indicatedin Scheme 2 and are thereafter set forth in the indicated paragraphswith the experimental data. The compound numbers are shown with doubleunderlining. All syntheses were done under an atmosphere of nitrogen orargon. Solvents were distilled under nitrogen prior to use. Concentratedsulfuric acid for the sulfonation of phosphines was used as received.2,2'-bis(trifluoromethanesulfonyloxy)-1,1'-binaphthalene was made by aliterature method 18!. ##STR15## EWG means electron withdrawing groupExample 1 encompasses steps 1, 2 a & b, 3 and 4

Example 3 encompasses steps 1, 5 and 6

EXAMPLE 1 Step 1 (Scheme 2) The Synthesis of Dip3-phenylpropyl)phenyl!chlorophosphine, 1

p-(3-phenylpropyl)phenyllithium (8.1 g, 40 mmol) in 150 ml solvent (Et₂O/THF 1/1) was added dropwise to CH₃ OPCl₂ (2.66 g, 20 mmol) in 70 mlsolvent (Et₂ O/THF 1/1) at -70° C. The addition was completed in 2 h.The reaction mixture was stirred overnight at room temperature and thenbrought to reflux for 2 h. The precipitate was filtered and the solventof the solution was removed by applying vacuum. PCl₃ (15 ml) was addedto the resulting viscous oil and stirred for 24 h. Then the mixture waskept at 70° C. and 1 mm Hg for 2 h to remove excess PCl₃ and byproduct.The product, di p-(3-phenylpropyl)phenyl!chlorophosphine, was obtainedas a pale yellow viscous oil with 90% yield. The product wascharacterized by ³¹ P NMR. 83.6.

Step 2 A (Scheme 2) The Synthesis of Dip-(3-phenylpropyl)phenyl!phosphine, 2

Di p-(3-phenylpropyl)phenyl!chlorophosphine 1 (6.0 g, 13.1 mmol) wasdissolved in 150 ml THF and Li (0.185 g, 26.2 mmol) was chopped directlyinto the reaction flask under Ar. A deep red solution was resulted in 10min and all the lithium was consumed in 4 h. The solvent was removed byvacuum and 100 ml diethyl ether was added. The organic phase was washed3×20 ml H₂ O and dried over MgSO₄. Ether was then removed by vacuum andthe final product was obtained as a pale yellow oil with quantitativeyield. 2 was characterized by ³¹ P NMR. -42.5, 'J_(H-P) =211 Hz.

Step 2 B (Scheme 2)

Finely chopped lithium metal (0.14 g, 0.02 mol) is suspended in 10 mLdry THF and tris-p-(3-phenylpropyl)phenylphosphine 9 (6.2 g, 0.01 mol)in 100 mL THF is added from a dropping funnel over a period of about 10minutes with vigorous stirring. The resulting deep red solution isstirred at room temperature for an additional 2 hours. Tertiarybutylchloride (0.93 g, 0.01 mol) is added and the reaction mixture isbrought to reflux for 15 minutes. The volume of the solution is reducedto about 10 mL and 80 mL dry degassed pentane is added. The reactionflask is then cooled to -78° C. to yield a dark red viscous residue anda colorless liquid. After decanting the colorless liquid, the residue 2is redissolved in 50 mL THF {³¹ P NMR (THF): -25.97}. The resultinganion can be used in subsequent synthesis that call for .sup.⊖ PAr₂, forinstance in Step 5 (Scheme 2). ##STR16##

Step 3 (Scheme 2) The Synthesis of 2.2'-Bis{dip-(3-phenylpropyl)phenyl!phosphine}-1,1'-binaphthalene 4

The synthesis was carried out by the reaction of2,2'-bis(trifluoromethanesulfonyloxy)-1,1'-binaphthalene, 3, with Dip-(3-phenylpropyl)phenyl!phosphine, 2, to yield 2,2'-Bis{dip-(3-phenylpropyl)phenyl!phosphine}-1,1'-binaphthalene, 4.

Compound 2 (0.48 g, 1.15 mmol) was added to a solution of NiCl₂ (dppe)(0.106 g, 0.2 mmol) in 5 ml DMF at room temperature. The resultingmixture was placed in an oil bath which had been preheated to 100° C. 30min later a solution of 3 (1.1 g, 2.0 mmol) and DABCO (0.9 g, 8.0 mmol)in 6 ml DMF was added at once. The color of the solution changedimmediately to dark brown. Three additional portions of 2 (0.5 g each)were added to the reaction mixture at 1, 3, and 7 h. The solution waskept at 100° C. for 4 days. Most of DMF was removed by vacuumdistillation and 40 ml diethyl ether was added to dissolve the organicproduct. After being washed with 2×20 ml H₂ O, either was removed toyield a brown viscous oil. The final product, 4, was separated as ayellow waxy solid from the oil by silica gel column usinghexane/diethylether (10/1). The overall yield of the reaction is 45%. 4was characterized by ¹ H, ¹³ C, ³¹ P NMR and Mass spectrometry.

Analytical data for BINAP-C3 ¹ HNMR (6 in CDCl₃) 1.87 (m, 8H); 2.53 (m,8H); 2.59 (m, 8H); 6.7-7.9 (m, 48H).

¹³ CNMR (δ in CDCl₃) 32.73 (s, 4C); 35.13 (s, 4C); 35.41 (d,⁵ J_(c-p)=10.1 Hz, 4C); 125.58 (s, 2C); 125.71 (s, 4C); 126.24 (s, 2C); 127.51(s, 2C); 127.91 (s, 2C); 128.16 (s, 4C); 128.26 (s, 8C); 128.41 (s, 8C);132.92 (*t, 8C); 133.30 (s,2C); 134.26 (*t, 8C); 135.10 (d, ¹ J_(c-p)=15.1 Hz, 4C); 136.12 (d, ¹ J_(c-p) =10.2 Hz, 2C); 141.61 (s, 2C);142.24 (d, ⁴ J_(c-p) =3.8 Hz, 4C); 142.50 (s, 4C).

³¹ PNMR (δ in CDCl₃) -16.3 (s)

Mass Spectroscopy (FAB, on phosphine oxide) 1127 (M⁺ +1)

Step 4 (Scheme 2) Synthesis of 2,2'-Bis{dip-(3-p-sulfonatophenylpropyl)phenyl!phosphino}-1,1'-binaphthalene, 5(=BINAP-C₃ -TS)

Compound 4 (1.0 g, 0.9 mmol) was chilled to -78° C. and 8 ml H₂ SO₄(96.1%) was added. The mixture was then allowed to be stirred at roomtemperature. 10 h later the mixture was neutralized with aqueous NaOH(20%, w/w). The final pH was 8.5. 320 ml of methanol was added and themixture was brought to reflux for 30 min. The precipitate, NaSO₄, wasthen filtered and the salt was washed with 100 ml hot methanol. Twoportions of the solution were combined and the volume was reduced to 20ml. 200 ml of acetone was then added to generate a white precipitate.The precipitate, 5, was collected by filtration and dried under vacuum(1.3 g, 95% yield). 5, was characterized by ¹ H, ¹³ C, ³¹ P NMR and Massspectrometry.

Analytical data for BINAP-C3-TS ¹ HNMR (δ in CD₃ OD) 1.86 (m, 8H); 2.53(m, 8H); 2.61 (m, 8H); 6.6-7.9 (m, 44H).

¹³ CNMR (δ in CD₃ OD) 33.87 (s, 4C); 36.09 (br.s, 8C); 126.28 (s, 2C);127.13 (s, 8C); 128.38 (s, 2C), 128.75 (s, 2C); 128.88 (s, 2C), 129.32(br.s, 12C); 134.25 (*t, 8C); 135.44 (*t, 8C); 136.50 (s, 2C); 137.25(s, 2C); 142.20 (s, 2C); 143.26 (s, 4C); 144.04 (s, 4C); 146.11 (s, 4C).

³ CNMR (δ in CD₃ OD) -15.2 (s)

Mass Spectroscopy (FAB, in glycerol matrix) 1525 (M⁺ +Na⁺)

EXAMPLE 2

Using the procedures outlined in Example 1, steps 2, 3 and 4, thefollowing steps were conducted in order to prepare the chiral form ofBINAP-C₃ -TS.

Example 2/Step 1 The Synthesis of2,2'-bis(trifluoromethanesulfonyloxy)-1,1'-binaphthalene(2)

Starting from commercial available (R)-(+)-1,1'-binaphthalene-2,2'-diol,(R)-(-)-2,2'-bis(trifluoromethanesulfonyloxy)-1,1'-binaphthalene (7) wasmade in one step according to a literature method 18!. The yield of thereaction is 62%.

Example 2/Step 2 The Synthesis of (R)-(+)-2,2'-Bis{dip-(3-p-sulfonatophenylpropyl)phenol!phosphino}-1,1'-binaphthalene (6)

The synthesis was carried out according to Cai's Ni catalyzed couplingfor the synthesis of 2,2'-bisdiphenylphosphino-1,1'-binaphthyl reference19!. The reaction of2,2'-bis(trifluoromethanesulfonyloxy)-1,1'-binaphthalene (7) with Dip-(3-phenylpropyl)phenyl!phosphine (2) gives 2,2'-Bis{dip-(3-phenylpropyl)phenyl!phosphino}-1,1'-binaphthalene 6. ##STR17##

7 and 2 are coupled in the presence of NiCl₂ (dppe)(dppe=1,2-bis(diphenylphosphino)ethane) and 1,4-diazabicyclo2.2.2!octane (DABCO) in anhydrous DMF at 100° C. Reaction is complete in3-4 days. The progress of the reaction is monitored by ³¹ P NMR. Theproduct, (R)-(+)-2,2'-Bis{di p-3-phenylpropyl)phenyl!phosphino}-1,1'-binaphthalene (6), is separated by silica gelcolumn using hexane/diethylether (10/1). The overall yield of thereaction is 45%.

The optical purity of 6 is checked by the ³¹ P NMR spectrum of2,2'-Bis{di p-(3-phenylpropyl)phenyl!phosphino}-1,1'-binaphthyl(S)-N,N-dimethyl-(1-phenylethyl)amine-2C,N!palladium(II). Only (R)-(+)-6is observed. The spectrum is ³¹ PNMR (δ in CDCl₃) d.d, 20.35, J_(p-p)=43.1 Hz J_(Pd-p) =2146.0 Hz.

Example 2/Step 3 Direct Sulfonation of (R-(+)-2,2'-Bis{dip-(3-phenylpropyl)phenyl!phosphino}-1,1'-binaphthalene (6)

The sulfonation of 6 is accomplished by H₂ SO₄ (96%) in 10 hours.Tetrasulfonated product (10) is obtained by precipitation with acetonein minimum amount of water. The yield of sulfonation is 95%. ##STR18##

EXAMPLE 3 Step 5 (Scheme 2) The Synthesis of 2,2'-Bis{dip-(3-phenylpropyl)phenyl!phosphinomethyl}-1,1-biphenyl, 11

Di p-(3-phenylpropyl)phenyl!chlorophosphine 1 (6.0 g, 13.1 mmol) wasdissolved in 150 ml THF and Li (0.185 g, 26.2 mmol) was chopped directlyinto the reaction flask under Ar. A deep red solution was resulted in 10min and all the lithium was consumed in 4 h. The solution was thenfiltered and 2,2'-dibromomethyl-1,1'-biphenyl (2.23 g, 6.5 mmol) in 20ml THF was added dropwise with an ice-water bath. The color of thesolution was slowly changed to pale yellow. The mixture was stirred foradditional 10 h before the solvent was removed by vacuum. 50 ml diethylether was added and it was washed with 3×10 ml H₂ O. The ether phase wasdried over MgSO₄ and the solvent was then removed by vacuum. Theresulting pale yellow viscous oil was purified over silica gel column.2.3 g (69% yield) of 11 was eluted with Et₂ O/hexane (1/10), 11 wascharacterized by ¹ H, ¹³ C, ³¹ P NMR and Mass spectrometry.

Analytical data for BISBI-C3 ¹ HNMR (δ in CDCl₃) 1.83 (m, 8H); 2.51 (m,16H); 3.06 (*quart, 4H); 6.9-7.2 (m, 44H).

¹³ CNMR (δ in CDCl₃) 32.72 (d, ⁷ J_(c-p) =3.7 Hz, 4C); 33.65 (d, ¹J_(c-p) =16.1 Hz, 2C); 35.12 (d, ⁶ J_(c-p) =2.3 Hz, 4C); 35.31 (d, ⁵J_(c-p) =13.0 Hz, 4C); 125.71 (s, 4C); 128.26 (s, 4C); 128.33 (s, 8C),128.36 (s, 8C); 129.65 (s, 2C); 129.75 (s, 2C); 132.64 (d, ³ J_(c-p)=18.3 Hz, 8C); 133.25 (d, ² J_(c-p) =19.1 Hz, 8C); 135.18 (d, ¹ J_(c-p)=14.5 Hz, 4C); 135.88 (d, ³ J_(c-p) =9.2 Hz, 2C); 140.82 (d, ² J_(c-p)=4.5 Hz, 2C); 142.09 (s, 4C); 142.44 (s, 4C).

³¹ PNMR (δ in CDCl₃) -11.8 (s)

Mass Spectroscopy (FAB, on phosphine oxide) 1055(M⁺ +1)

EXAMPLE 3 Step 6 (Scheme 2) Synthesis of tetrasulfonated 2,2'-Bis{dip-(3-phenylpropyl) phenylphosphinomethyl}-1,1'-biphenyl, 12(=BISBI-C₃-TS)

2,2'-Bis{di p-(3-phenylpropyl)phenyl!phosphinomethyl}-1,1'-biphenyl, 11(2.2 g, 2.2 mmol), was dissolved in eight ml H₂ SO₄ (96%) with anice-water bath. The brown solution was stirred at room temperature for 7h. The mixture was then neutralized by 20% (w/w) aqueous NaOH. The finalpH was 8.5. 320 ml of methanol was added and the mixture was brought toreflux for 30 min. The precipitate, NaSO₄, was then filtered and thesalt was washed with 100 ml hot methanol. Two portions of the solutionwere combined and the volume was reduced to 20 ml. 200 ml of acetone wasthen added to generate a white precipitate. The precipitate, sulfonated2,2'-Bis{di p-(3-phenylpropyl) phenyl!phosphinomethyl}-1,1'-biphenyl,12, was collected by filtration and dried under vacuum (2.8 g, 93%yield). 12 was characterized by ¹ H, ¹³ C, ³¹ p NMR and Massspectrometry.

Analytical data for BISBI-C3-TS ¹ HNMR (δ in CD₃ OD) 1.91 (m, 8H); 2.57(m, 8H); 2.63 (m, 8H); 3.10 (*quart, 4H); 6.8-7.8 (m, 40H).

¹³ CNMR (δ in CD₃ OD) 34.12 (d, ¹ J_(c-p) =13.1 Hz, 2C); 34.15 (s, 4C);36.13 (s, 4C); 36.20 (s, 4C); 127.08 (s, 8C); 129.36 (s, 8C); 129.77 (s,4C); 130.70 (s, 2C); 130.75 (s, 2C); 133.75 (d, ³ J_(c-p) =18.3 Hz, 8C);134.51 (d, ² J_(c-p) =19.8 Hz, 8C); 143.92 (s, 4C); 146.15 (s, 4C).

³¹ PNMR (δ in CD₃ OD) -10.7 (s)

Mass Spectroscopy (FAB, in glycerol matrix) 1453 (M⁺ +Na⁺)

EXAMPLES 4 and 5

Two Phase Catalysis with 2,2'-Bis{dip-(3-p-sulfonatophenylpropyl)phenyl!phosphino}-1,1'-binaphthalene(BINAP-C₃ -TS) 5 and 2,2'-Bis{dip-(3-p-sulfonatophenylpropyl)phenyl!phosphinomethyl}-1,1'-biphenyl(BISBI-C₃ -TS) 12.

EXAMPLE 4 Two phase hydroformylation of 1-octene with BINAP-C₃ -TS andBISBI-C₃ -TS

Two phase hydroformylation of 1-octene with BISBI-C₃ -TS and BINAP-C₃-TS was carried out in a 30 ml stainless steel reaction vessel. Thecatalyst was made in situ by mixing 0.76 ml 0.01M Rh(acac)(CO)₂ inmethanol and the required amount of 0.1M aqueous solution of ligand.Water was added to adjust the total aqueous methanol volume to 1.56 ml.The substrate, 0.60 ml of 1-octene, was then transferred into thereaction vessel under positive pressure of CO. Nonane, 0.40 ml, wasadded as an internal standard for gas chromatography analysis.Therefore, the volume of organic phase is 1.0 ml. The octene/Rh ratiowas 500/1 in all catalytic runs. After the reaction vessel was loadedand pressurized with CO/H₂ to 210 psi, the reaction was initiated byplacing the reaction vessel into a temperature bath preheated to 120° C.The reaction mixture was constantly stirred with a magnetic stir bar at350 rpm. Catalytic reactions were terminated by removing the vessel fromthe oil bath and depressurizing when it had been cooled in an ice-waterbath. In all cases the organic layer was colorless and readily separatedfrom aqueous layer after the reaction.

The reaction product distribution was analyzed by gas chromatography ona Varian 3300 gas chromatograph equipped with a HP1 column 25 m×0.32mm×0.52 μm, and FID detector, He was the carrier gas; the temperatureprogram was from 35° C. (4 min) to 220° C. (1 min), at a heating rate of10° C./min. A special injection port sleeve was installed to facilitatethe separation of analytes which have very close boiling points.

Hydroformylation results of 1-octene with BISBI-C₃ -TS and BINAP-C₃ -TSare summarized in Table 1. For comparison, results from two phasehydroformylation of 1-octene with TPPTS under the same reactionconditions is also listed. The aqueous solution consists of 50% H₂ O and50% methanol. The presence of methanol is due to the preparation of insitu catalyst. Leakage of methanol into the organic phase after thereaction is less than 0.5%. Concentration of Rh in both the organic andaqueous phases was checked by ICP method (Table 2). The detection limitis ˜1/3 ppm. The organic phase after the reaction is without color andRh is not detected by ICP, which since the sample is diluted, sets alower limit of 3 ppm on Rhodium in the organic phase if it indeed ispresent.

At ligand/Rh ratio of 7-9, the rhodium catalyst with BISBI-C₃ -TS offersgood reactivity and selectivity towards 1-nonanal. Detailed productdistribution is given in Table 2. Increased activity, compared to theRh/TPPTS system, is understandably explained by the surface activity ofthe ligand.

                  TABLE I                                                         ______________________________________                                        Two Phase Hydroformylation of 1-octene                                        with BISBI-C.sub.3 -TS, BINAP-C.sub.3 -TS and TPPTS                           TPPTS          BISBI-C3-TS  BINAP-C3-TS                                       Rh/P  Yield  n/b       Yield                                                                              n/b     Yield                                                                              n/b                                  ratio (%)    (%/%)     (%)  (%/%)   (%)  (%/%)                                ______________________________________                                        1:2   30     68/32     45   68/32   29   74/26                                1:3   37     70/30     57   76/24   31   74/26                                1:5   52     75/25     69   88/12   14   75/25                                1:7   54     76/24     73   94/6     5.3 70/30                                1:9   69     76/24     67   97/3    --   --                                    1:14 --     --        30   98/2    --   --                                   ______________________________________                                    

Reaction Conditions: reaction time, 5 h; reaction temperature, 120° C.;initial pressure, 210 psi (at 25° C.); stirring rate is 350 rpm;Rh!=0.0049M.

                  TABLE 2                                                         ______________________________________                                        Results From Two Phase Hydroformylation of Octene-I                           at Rh/Phosphorus = 1/7. Product Distribution                                                   TPPTS     BISBI--C.sub.3 --TS                                ______________________________________                                        yield of C.sub.9 58ldehydes (%)                                                                          74                                                 selectivity (% of 1-nonanal)                                                                   74        93                                                 C.sub.8 hydrocarbons (%)                                                                       34        23                                                  % of 1-octene!    5!       14!                                               C.sub.9 alcohols (%)                                                                           7.1       2.5                                                heavy ends (%)   0.8       0.2                                                 Rh! in organic phase (ppm)                                                                    not detected                                                                            not detected                                        Rh! in aqueous phase (ppm)                                                                    508       514                                                ______________________________________                                    

Reaction conditions: Rh!=502 ppm, Rh/octene-1=1/500, Temperature=120°C., Pressure=210 psi at room temperature, Reaction time=5 h, Stirringrate=350 rpm, The Rh! is determined by ICP method. Both standard andsamples are prepared in MeOH.

EXAMPLE 6 Two phase asymmetric hydrogenation of acetophenoneN-benzylimine with (R)-(+)-BINAP-C₃ -TS (6)

Hydrogenation of acetophenone N-benzylimine with (R)-(+)-BINAP-C₃ -TS(6) is carried out under two phase conditions with ethyl acetate as theorganic solvent. ##STR19##

The catalyst is made in situ by mixing Rh(COD)Cl!₂ with water solubleligand in water. The substrate, acetophenone N-benzylimine, is dissolvedin ethyl acetate and charged to the reactor after the catalyst istotally dissolved in water, which takes about 10 min. The reactor isthen pressurized to 1000 psi of H₂. The reaction temperature is 25° C.and the reaction time is 41.5 hours. The same catalysis withRh/tetrasulfonated (2S, 4S)-bis-(diphenylphosphino)pentane (BDPPTS) isalso done for comparison. The conversion is checked by GC-MS and ¹ HNMR. The optical purity of the product is determined by ¹ H NMR using2,2,2-trifluoro-1-(9-anthryl)ethanol as shift reagent.

                  TABLE 3                                                         ______________________________________                                        Asymmetric Hydrogenation of acetophenone N-benzylimine                        with (R)-(+)-BINAP--C.sub.3 --TS and (2S, 4S)-BDPPTS                          Ligand           Yield (%)                                                                              e.e. (%)                                            ______________________________________                                        BINAP--C.sub.3 --TS                                                                            98       56                                                  BDPPTS           45       29                                                  ______________________________________                                    

Compared to Rh/BDPPTS catalyst, rhodium catalyst with BINAP-C₃ -TSoffers increased activity and selectivity.

Asymmetric hydrogenation with (R)-(+)-BINAP-C₃ -TS

According to Example 6, 2-(4-isobutylphenyl) propanoic acid and themethyl ester of acetylaminocinnamic acid were asymmetricallyhydrogenated with the Rh- or Ru complexes of (R)-(+)-BINAP-C₃ -TS (Table4).

                  TABLE 4                                                         ______________________________________                                        Asymmetric Catalysis Results with (R)-(+)-BINAP-C.sub.3 -TS                                                Con-    e. e                                     Catalyst  Substrate          version (%)                                      ______________________________________                                        Ru/BINAP-C.sub.3 -TS                                                                    2-(4-isobutylphenyl)propenoic acid                                                               100     19                                       Rh/BINAP-C.sub.3 -TS                                                                     ##STR20##         100     16                                       ______________________________________                                    

The quantitative conversion of substrates clearly proves the concept ofsurface active ligands, which allow catalytic reaction in a two-phasemedia like water-insoluble substrates.

Although the invention has been illustrated by certain of the precedingexamples, it is not to be construed as being limited thereby; butrather, the invention encompasses the generic area as hereinbeforedisclosed. Various modifications and embodiments can be made withoutdeparting from the spirit and scope thereof.

What is claimed is:
 1. An aryl diphosphine having the formula ##STR21##wherein: (a) X and Y are each independently selected from the groupconsisting of alkyl C₁ -C₂₀, alkenyl C₁ -C₂₀, alkynyl C₁ -C₂₀, phenyl,naphthyl, --NR--, oxygen and sulfur;(b) m and m' are each separateintegers of 0 or 1; (c) R₁ -R₈ are each independently selected from thegroup consisting of hydrogen, halogen, nitro, amino, alkyl C₁ -C₂₀,alkoxy, hydroxy, --C(O)--OR, --CN, --N.sup.⊕ (R)₃ X.sup.⊕, and aryl; (d)R₁ and R₂, R₂ and R₃, R₃ and R₄, R₅ and R₆, R₆ and R₇, R₇ and R₈ mayalso (in addition to the above) form a cyclic ring containing a total of2 to 6 atoms selected from the group consisting of carbon atoms, oxygenatoms, nitrogen atoms, sulfur atoms, and mixtures thereof, with theproviso that said ring can be substituted or unsubstituted; (e) R₉ -R₁₂and R₁₄ -R₁₈ are each independently selected from the group consistingof hydrogen, halogen, --SO₃ M, alkyl C₁ -C₂₀, --CO₂ M, --N.sup.⊕ (R)₃X.sup.⊖, --CN, --OR, --C(O)--OR, and --P(R)₂ ; (f) R₁₃ is selected fromthe group consisting of a straight chain or branched chain alkyl C₁-C₂₀, alkenyl C₁ -C₂₀, alkynyl C₁ -C₂₀, phenyl, naphthyl, anthracyl, andsubstituted phenyl, naphthyl, and anthryl; and (g) n is an integer from1 to 20; whereM is selected from the group consisting of alkali metal,alkaline earth metals, and N(R)₄.sup.⊕, R is H, alkyl C₁ -C₂₀ or phenyl,and X.sup.⊖ is a halide.
 2. The aryl diphosphine of claim 1 wherein M isselected from the group consisting of Na, K, Li, Rb, Cs, Mg, Ca and NH₄.3. The aryl diphosphine of claim 1 wherein n is
 3. 4. The aryldiphosphine of claim 1 wherein m is
 0. 5. The aryl diphosphine of claim1 wherein at least one of R₉ -R₁₂ and R₁₄ -R₁₈ is --SO₃ M.
 6. Awater-soluble aryl diphosphine having the formula ##STR22## wherein n isan integer of 1 to 10 and M is an alkali metal.
 7. A water-soluble aryldiphosphine having the formula ##STR23## wherein n is an integer of 1 to10.
 8. A composition of matter having the formula ##STR24## wherein: (a)X and Y are each independently selected from the group consisting ofalkyl C₁ -C₂₀, alkenyl C₁ -C₂₀, alkynyl C₁ -C₂₀, phenyl, naphthyl,--NR--, oxygen and sulfur;(b) m and m' are each separate integers of 0or 1; (c) R₁ -R₈ are each independently selected from the groupconsisting of hydrogen, halogen, nitro, amino, alkyl C₁ -C₂₀, alkoxy,hydroxy, --C(O)--OR, --CN, --N.sup.⊕ (R)₃ X.sup.⊖, and aryl; (d) R₁ andR₂, R₂ and R₃, R₃ and R₄, R₅ and R₆, R₆ and R₇, R₇ and R₈ may also (inaddition to the above) form a cyclic ring containing a total of 2 to 6atoms selected from the group consisting of carbon atoms, oxygen atoms,nitrogen atoms, sulfur atoms, and mixtures thereof, with the provisothat said ring can be substituted or unsubstituted; (e) R₉ -R₁₂ and R₁₄-R₁₈ are each independently selected from the group consisting ofhydrogen, halogen, --SO₃ M, alkyl C₁ -C₂₀, --CO₂ M, --N.sup.⊕ (R)₃X.sup.⊖, --CN, --OR, --C(O)--OR, and --P(R)₂ ; (f) R₁₃ is selected fromthe group consisting of a straight chain or branched chain alkyl C₁-C₂₀, alkenyl C₁ -C₂₀, alkynyl C₁ -C₂₀, phenyl, naphthyl, anthracyl, andsubstituted phenyl, naphthyl, and anthryl; (g) n is an integer from 1 to20; (h) M' is selected from the group consisting of manganese, cobalt,nickel, chromium, iron, rhenium, ruthenium, rhodium, technetium,palladium, platinum, osmium, copper, cadmium, indium, tungsten,molybdenum, mercury, gold and silver; (i) L is a ligand which can bebound to M'; and (j) x is an integer of 0 to 7; whereM is selected fromthe group consisting of alkali metal, alkaline earth metals, andN(R)₄.sup.⊕, R is H, alkyl C₁ -C₂₀, or phenyl, and X.sup.⊖ is a halide.9. The composition of claim 8 wherein M is selected from the groupconsisting of Na, K, Li, Rb, Cs, Mg, Ca and NH₄.
 10. The composition ofclaim 8 wherein n is
 3. 11. The composition of claim 8 wherein m is 0.12. The composition of claim 8 wherein at least one of R₉ -R₁₂ and R₁₄-R₁₈ is --SO₃ M.
 13. The composition of claim 8 wherein L is selectedfrom the group consisting of CO, NO, PF₃, H₂ O, S, halogen, PF₆, CN,hydrides, BF₄, aromatic ligands, olefin ligands, acetylene ligands, andphosphine ligands.
 14. A composition of matter having the formula##STR25## wherein: (a) X and Y are each independently selected from thegroup consisting of alkyl C₁ -C₂₀, alkenyl C₁ -C₂₀, alkynyl C₁ -C₂₀,phenyl, naphthyl, --NR--, oxygen and sulfur;(b) m and m' are eachseparate integers of 0 or 1; (c) R₁ -R₈ are each independently selectedfrom the group consisting of hydrogen, halogen, nitro, amino, alkyl C₁-C₂₀, alkoxy, hydroxy, --C(O)--OR, --CN, --N.sup.⊕ (R)₃ X.sup.⊕, andaryl; (d) R₁ and R₂, R₂ and R₃, R₃ and R₄, R₅ and R₆, R₆ and R₇, R₇ andR₈ may also (in addition to the above) form a cyclic ring containing atotal of 2 to 6 atoms selected from the group consisting of carbonatoms, oxygen atoms, nitrogen atoms, sulfur atoms, and mixtures thereof,with the proviso that said ring can be substituted or unsubstituted; (e)R₉ -R₁₂ and R₁₄ -R₁₈ are each independently selected from the groupconsisting of hydrogen, halogen, --SO₃ M, alkyl C₁ -C₂₀, --CO₂ M,--N.sup.⊕ (R)₃ X.sup.⊖, --CN, --OR, --C(O)--OR, and --P(R)₂ ; (f) R₁₃ isselected from the group consisting of a straight chain or branched chainalkyl C₁ -C₂₀, alkenyl C₁ -C₂₀, alkynyl C₁ -C₂₀, phenyl, naphthyl,anthracyl, and substituted phenyl, naphthyl, and anthryl; (g) n is aninteger from 1 to 20; (h) M' is selected from the group consisting ofmanganese, cobalt, nickel, chromium, iron, rhenium, ruthenium, rhodium,technetium, palladium, platinum, osmium, copper, cadmium, indium,tungsten, molybdenum, mercury, gold and silver; (i) L is a ligand whichcan be bound to M'; and (j) x is an integer of 0 to 7; whereM isselected from the group consisting of alkali metal, alkaline earthmetals, and N(R)₄.sup.⊕, R is H, alkyl C₁ -C₂₀, or phenyl, and X.sup.⊖is a halide.
 15. The composition of claim 14 wherein L is selected fromthe group consisting of CO, NO, PF₃, H₂ O, S, halogen, PF₆, CN,hydrides, BF₄, aromatic ligands, olefin ligands, acetylene ligands, andphosphine ligands.
 16. The composition of claim 14 wherein M is selectedfrom the group consisting of Na, K, Li, Rb, Cs, Mg, Ca and NH₄.
 17. Thecomposition of claim 14 wherein n is
 3. 18. The composition of claim 14wherein m is
 0. 19. The composition of claim 14 wherein at least one ofR₉ -R₁₂ and R₁₄ -R₁₈ is --SO₃ M.
 20. An aryl diphosphine having theformula ##STR26## wherein: (a) X and Y are each independently selectedfrom the group consisting of alkyl C₁ -C₂₀, alkenyl C₁ -C₂₀, alkynyl C₁-C₂₀, phenyl, and naphthyl;(b) m and m' are each separate integers of 0or 1; (c) R₁ -R₈ are each independently selected from the groupconsisting of hydrogen, halogen, nitro, amino, alkyl C₁ -C₂₀, alkoxy,hydroxy, --C(O)--OR, --CN, --N.sup.⊕ (R)₃ X.sup.⊕, and aryl; (d) R₁ andR₂, R₂ and R₃, R₃ and R₄, R₅ and R₆, R₆ and R₇, R₇ and R₈ may also (inaddition to the above) form a cyclic ring containing a total of 2 to 6atoms selected from the group consisting of carbon atoms, oxygen atoms,nitrogen atoms, sulfur atoms, and mixtures thereof, with the provisothat said ring can be substituted or unsubstituted; (e) R₉ -R₁₂ and R₁₄-R₁₈ are each independently selected from the group consisting ofhydrogen, halogen, --SO₃ M, alkyl C₁ -C₂₀, --CO₂ M, --N.sup.⊕ (R)₃X.sup.⊖, --CN, --OR, --C(O)--OR, and --P(R)₂ ; (f) R₁₃ is selected fromthe group consisting of a straight chain or branched chain alkyl C₁-C₂₀, alkenyl C₁ -C₂₀, alkynyl C₁ -C₂₀, phenyl, naphthyl, anthracyl, andsubstituted phenyl, naphthyl, and anthryl; and (g) n is an integer from1 to 20; whereM is selected from the group consisting of alkali metal,alkaline earth metals, and N(R)₄.sup.⊕, R is H, alkyl C₁ °C₂₀, orphenyl, and X.sup.⊕ is a halide.
 21. A composition of matter having theformula ##STR27## wherein: (a) X and Y are each independently selectedfrom the group consisting of alkyl C₁ C₂₀, alkenyl C₁ -C₂₀, alkynyl C₁°C₂₀, phenyl, and naphthyl;(b) m and m' are each separate integers of 0or 1; (c) R₁ -R₈ are each independently selected from the groupconsisting of hydrogen, halogen, nitro, amino, alkyl C₁ -C₂₀, alkoxy,hydroxy, --C(O)--OR, --CN, --N.sup.⊕ (R)₃ X.sup.⊖, and aryl; (d) R₁ andR₂, R₂ and R₃, R₃ and R₄, R₅ and R₆, R₆ and R₇, R₇ and R₈ may also (inaddition to the above) form a cyclic ring containing a total of 2 to 6atoms selected from the group consisting of carbon atoms, oxygen atoms,nitrogen atoms, sulfur atoms, and mixtures thereof, with the provisothat said ring can be substituted or unsubstituted; (e) R₁ -R₁₂ and R₁₄-R₁₈ are each independently selected from the group consisting ofhydrogen, halogen, --SO₃ M, alkyl C₁ -C₂₀, --CO₂ M, --N.sup.⊕ (R)₃X.sup.⊖, --CN, --OR, --C(O)--OR, and --P(R)₂ ; (f) R₁₃ is selected fromthe group consisting of a straight chain or branched chain alkyl C₁--C₂₀, alkenyl C₁ -C₂₀, alkynyl C₁ -C₂₀, phenyl, naphthyl, anthracyl,and substituted phenyl, naphthyl, and anthryl; (g) n is an integer from1 to 20; (h) M' is selected from the group consisting of manganese,cobalt, nickel, chromium, iron, rhenium, ruthenium, rhodium, technetium,palladium, platinum, osmium, copper, cadmium, indium, tungsten,molybdenum, mercury, gold and silver; (i) L is a ligand which can bebound to M'; and (j) x is an integer of 0 to 7; whereM is selected fromthe group consisting of alkali metal, alkaline earth metals, andN(R)₄.sup.⊕, R is H, alkyl C₁ -C₂₀, or phenyl, and X.sup.⊖ is a halide.22. A composition of matter having the formula ##STR28## wherein: (a) Xand Y are each independently selected from the group consisting of alkylC₁ -C₂₀, alkenyl C₁ C₂₀, alkynyl C₁ -C₂₀, phenyl, and naphthyl;(b) m andm' are each separate integers of 0 or 1; (c) R₁ -R₈ are eachindependently selected from the group consisting of hydrogen, halogen,nitro, amino, alkyl C₁ -C₂₀, alkoxy, hydroxy, --C(O)--OR, --CN,--N.sup.⊕ (R)₃ X.sup.⊖, and aryl; (d) R₁ and R₂, R₂ and R₃, R₃ and R₄,R₅ and R₆, R₆ and R₇, R₇ and R₈ may also (in addition to the above) forma cyclic ring containing a total of 2 to 6 atoms selected from the groupconsisting of carbon atoms, oxygen atoms, nitrogen atoms, sulfur atoms,and mixtures thereof, with the proviso that said ring can be substitutedor unsubstituted; (e) R₉ -R₁₂ and R₁₄ -R₁₈ are each independentlyselected from the group consisting of hydrogen, halogen, --SO₃ M, alkylC₁ -C₂₀, --CO₂ M, --N.sup.⊕ (R)₃ X.sup.⊖, --CN, --OR, --C(O)--OR, and--P(R)₂ ; (f) R₁₃ is selected from the group consisting of a straightchain or branched chain alkyl C₁ -C₂₀, alkenyl C₁ -C₂₀, alkynyl C₁ -C₂₀,phenyl, naphthyl, anthracyl, and substituted phenyl, naphthyl, andanthryl; (g) n is an integer from 1 to 20; (h) M' is selected from thegroup consisting of manganese, cobalt, nickel, chromium, iron, rhenium,ruthenium, rhodium, technetium, palladium, platinum, osmium, copper,cadmium, indium, tungsten, molybdenum, mercury, gold and silver; (i) Lis a ligand which can be bound to M'; and (j) x is an integer of 0 to 7;whereM is selected from the group consisting of alkali metal, alkalineearth metals, and N(R)₄.sup.⊕, R is H, alkyl C₁ -C₂₀, or phenyl, andX.sup.⊖ is a halide.